Dynamic Kinetic Resolution of Aldehydes by Hydroacylation

Angew Chem Int Ed Engl. 2019 Mar 26;58(14):4705-4709. doi: 10.1002/anie.201900545. Epub 2019 Feb 27.

Abstract

We report a dynamic kinetic resolution (DKR) of chiral 4-pentenals by olefin hydroacylation. A primary amine racemizes the aldehyde substrate via enamine formation and hydrolysis. Then, a cationic rhodium catalyst promotes hydroacylation to generate α,γ-disubstituted cyclopentanones with high enantio- and diastereoselectivities.

Keywords: C−H activation; dual catalysis; dynamic kinetic resolution; hydroacylation; rhodium.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Acylation
  • Aldehydes / chemistry*
  • Alkenes / chemistry*
  • Catalysis
  • Cyclopentanes / chemical synthesis*
  • Cyclopentanes / chemistry
  • Hydrolysis
  • Kinetics
  • Molecular Structure
  • Rhodium / chemistry
  • Stereoisomerism
  • Thermodynamics*

Substances

  • Aldehydes
  • Alkenes
  • Cyclopentanes
  • cyclopentanone
  • Rhodium